JPH08510801A - Novel polyolefin fibers and their fabrics - Google Patents

Abstract

(57) Summary A new fiber containing reactor grade isotactic poly-alpha-olefins was produced. Here, polypropylene is produced by monodentate catalysis and has a melt flow rate greater than 0 to about 5,000 and an MWD of about 1.0 to about 3.5.

Description

Detailed Description of the Invention                     Novel polyolefin fibers and their fabricsField of the invention   The present invention is directed to isotactic polyolefin reactor grades. ), And new fabrics made from these fibers. These new fibers Fibers and cloths are manufactured from isotactic polyolefin. Isotactic polyolefins are post-reacted to reduce molecular weight (post-react Reactor-grade polymer useful for fiber formation, even if untreated or treated) Or was post-reacted without substantially changing the MWD of the polymer resin It is a thing.Background of the Invention   Poly-alpha-olefins have traditionally been used as titanium chlorides such as titanium chloride. Catalysis by known multi-site catalysts including Grahler-Natta type catalysts I received it. Such catalysts are used in the production of alpha olefins including polypropylene. Useful for the production of fats or polymers, but they have a relatively wide molecular weight distribution Or producing a polymer having polydispersity, such polymer being a polyolefin Polymers having a molecular weight higher than the average or nominal molecular weight of the polymer It contains a significant proportion of both substances and polymeric substances having a low molecular weight.   High molecular weight fraction contained in polymers produced by conventional catalysts Has processing problems for manufacturers of polypropylene fibers or fiber-containing products. Russ. Although not wishing to be bound by theory, such reactor grade poly The high molecular weight species of polypropylene found in the mer is the melt of the melted polypropylene. Contribution to strength significantly, polymer processability, especially in the field of fiber manufacturing Is considered to decrease. Made using multidentate catalysts or by other conventional methods The high melt strength of the produced fused polypropylene is generally shaped into fibers by melt spinning. Fibers of relatively large diameter that are made, but when operated at economically practical production rates To form Such fibers are smaller in diameter than other fibers, especially natural fibers. May feel stiff or coarse compared to squid or low denier fibers Absent.   Conceptually, within a production batch of a particular designation or average molecular weight, high molecular weight poly It is easy to imagine why it is desirable to reduce the concentration of propylene species. It's easy. Longer polymer chains are more conformationally bulkier Given that they tend to scoop, roll, or become entangled, these particular species It is understood that it becomes more immobile within the polymer. These high molecular weight chains are relatively The fact that it is long is due to the need for higher processing temperatures and the high It is the cause of strong strength. From a kinetic standpoint, enough to move these molecules Adding energy becomes even more difficult. Once these high molecular weight species dissolve When melted, they are generally more entangled due to their size. Fiber production speed In the case of melt spinning, for example, melt blowing or Is used in spun bonding for the subsequent production of high quality fabrics. It is the presence of this high proportion of high molecular weight species that causes a number of problems. .   Caused by or at least exacerbated by the high molecular weight fraction Are some of the problems associated with lowering the intrinsic melt strength and viscosity of moving high molecular weight chains. Therefore, a high processing temperature is required for this purpose. This includes high molecular weight seeds. High energy to move the polymer through the extruder or other processing equipment. -Requires input. All of this is necessary in material handling equipment, including extruders. Not only does it result in higher wear resulting from the higher energy required, It also leads to deterioration of the properties of the easy polymer and polymer products.   With respect to fibers, generally non-homopolyethylene with a significant proportion of high molecular weight species. Higher polyolefins are processed with some problems. Co-pending USSN 08/066, 737 (This application claims priority as a continuation-in-part application from this application) As noted, in addition to the general problems encountered during the processing of this material, other problems Occurs with the processing of the fiber. These problems are subtle at practical production rates. It is difficult to produce a good fiber, which is a molten polymer. This is because it is difficult to stretch the fibrils. This is a molten polyolefin The high melt strength of tin, especially the high melt strength of polypropylene containing high molecular weight species. to cause. High melt strength also makes molten resin smaller fiber forming orifice It also causes difficulties in pushing through. Within this limit, high molecular weight components The child creates considerable resistance and reduces flow. These same molecules also have conformations Inherent inclination to elastic response with recovery of conformal bulk Due to the orientation of the polymer fibrils as they exit the fiber forming orifice Causes swelling. Molten polypropylene is its nominal molecular weight Is responsible for having a much higher melt strength than expected from Is also a fraction of the same high molecular weight molecules. The net effect is again high molecular weight Due to the high melting temperature of the fraction and the high energy input to the equipment Yes, this is due to the high pressure required to push the material through the fiber forming orifice. The resulting high wear rate. High temperature and pressure inevitably fiber form Shorten the life of the forming die or spinneret.   In addition to these processing issues associated with fiber manufacturing, traditionally manufactured Fibers made from propylene tend to be thicker due to the melt strength of the molten resin There is. Such fibers allow the formation of a cloth that has a fairly boardy feel. Brings and stretches or blends in at flex points when worn as clothing Does not Roughness and "elasticity" in such poly-alpha-olefin fabrics Deficiency in clothing and other uses for which a pleasant feel or "texture" is desired. Limit the use of such cloths in   It is traditional to lead to some complex post-formation processes Made from catalytically produced polyolefins, especially polypropylene It is like a fiber board and a cloth board obtained from them. For example, Kobayashi ( Kobayoshi) et al., In US Pat. Some stretchability and reduction in the fabric when used as clothing with crimps A mechanical squeezing process that effectively imparts improved stiffness.   1970 in the field of post-reaction treatment to improve the processability of polypropylene There has been considerable progress. Most of these post-reaction and post-formation treatments It involves the breaking of certain chains of the polymer molecule. Such disruption or molecular cleavage is common. Ordinary polyolefins, especially polypropylene, heat and oxygen, or organic peroxides Is carried out by treatment with a radical source such as As conventional technology, these techniques Some of the techniques are U.S. Pat.Nos. 3,608,001, 3,563,972, 3,862,265, and 3 , 898,209.   Timmons et al., In US Pat. No. 5,188,885, disclosed polypropylene Is used to teach the formation of nonwoven laminates. Chimon as described The isotactic polypropylene used by Zu et al. Is of low crystalline nature. I.e., low isotacticity. Also, Timmons is their cloth Exxon Polymer Grades 3125 and 32 for forming 14 is used. 3214 grade is treated with peroxide It is clearly stated that the melt viscosity was lowered by the fragmentation. Although not specified , 3125 grade is a peroxide treated grade of polypropylene Must be understood. Polypropylene whose viscosity has been reduced by post-reaction treatment Len was used for half of the fabric laminate. The other half used was ethylene glycol It is a polymer, not a poly-alpha-olefin.   Such post-reaction treatment involves molecular cleavage or cleavage of all polymer chains within the polymer. It can cause overall degradation, which results in a difference between the nominal molecular weight and the polymer. The offspring distribution is dramatically reduced. Larger polyolefin molecules will be Of high molecular weight species in terms of having more potential sites for Fractions will be significantly reduced upon exposure of such resins to post-reaction treatments .   As mentioned above, post-reaction treatments including oxidative cleavage serve a useful purpose for fiber manufacturers. stand. Such fragmentation is more common than most other end-use product manufacturers. Manufactured by melt spinning, melt blowing, or spunbonding processes. It provides similar advantages to manufacturers of fibers and textile products containing the products described. these Include reduced overall viscosity, shift in molecular weight distribution, reduced nominal molecular weight, and high molecular weight. A fraction of high molecular weight species reduced in width is included.   However, the advantages that result from post-reaction oxidative cleavage of polypropylene are: It has some serious drawbacks. Such processing of polypropylene exists at high It actually significantly reduces the fraction of molecular weight species, but also Dramatically increase the fraction of offspring species. The presence of these low molecular weight species is It brings various difficulties to the manufacturer. Low molecular weight species tend to be more mobile As such, they also tend to become volatile during melt processing.   This volatility does not occur at high temperatures if it is not hermetically sealed as it exits the spinning die. It causes problems such as apparent fuming from the material. Due to volatility, unpleasant vapor A nuisance or odor may be produced by persons engaged in the manufacture and processing of fibers. It becomes a problem for the space. The same volatility of the low molecular weight fraction will cause the fiber to be drawn Tend to cause blooming or surface defects on post-finished fibers, which Potential pitting or cracking as low molecular weight species volatilize This is because. Low molecular weight species from the melt as it exits the forming equipment or die These low molecular weight species re-condense inside the ventilator when they volatilize and then return to the melting point. The contraction also causes maintenance problems.   Within the fiber production itself, the fraction of low molecular weight species increased. Other problems may occur depending on. This includes a considerable dripping from the die Or dripping, which is due to the separation of low molecular weight species at the exit of the die. It The decrease in viscosity is caused by the low molecular weight species. Orifi with the droop There is also a tendency for low molecular weight species to collect at the exit of the membrane or die. During high-speed machining, The gathered scale is the surface of the fiber formed off the die or spinneret surface Will be included in. This "slub" becomes a defect in the fiber, which is May cause breaks in the line. If such a slab occurs, The production line must be stopped. Replace the die before starting production again Must be done or cleaned.   Polymer manufacturers offer products treated by post-reaction oxidative cleavage process In essence, in order to take advantage of the processing of these polypropylenes, , End-use manufacturers have drawbacks caused by the presence of increased low molecular weight fraction Accept. Introduces other handling issues to the fiber or textile manufacturer In addition to that, polyolefin manufacturers have another fairly high A valuable process must be added. For polymer manufacturers, this is Not only increase the cost, but also complicate the process of manufacturing polyolefin resin. .   Of the added complications for polymer manufacturers and end users of polyolefins From a point of view, the raw material has a narrow molecular weight distribution and is oxidatively deteriorated by post-reaction treatment. Isotactic polyp as a reactor grade material with a nominal molecular weight of the product. Producing ropylene is useful and valuable. Polymer manufacturing process Besides eliminating costly and process-complex steps from the process, this It offers many advantages to end users, especially polyolefin fiber manufacturers.   Of particular value to textile manufacturers are smoke and odor issues, ventilation equipment. Stains and surface blooming on finished fibers. further 1) A narrow molecular weight centered around the nominal molecular weight A fabric, and 2) a polyolefin having the handling properties of an oxidatively degraded polyolefin. Fin products reduce processing problems, including drooling and slabs, which This not only improves the productivity of the fiber manufacturer's equipment, but also the quality of the product.   With the above-mentioned advantages, fiber manufacturers are more likely than they would be by oxidative degradation. It is possible to further lower the melt strength of the polymer. Smell in polypropylene containing a significant fraction of molecules with even higher molecular weight The diameter of the produced fiber with less die swell than that experienced It is possible. Such polymer products are expensive to polymer manufacturers. By eliminating the need for complex post-reaction processing steps, By providing the possibility of high speed production of finer fibers for both Provide benefits to.   Kloos is a conference held in September 1987, The Plastics an d Rubber Institute'sFourth International Conference on Polypropylene Fi bres and Textiles Published in “Dependence of Structure and Prope rty of Melt Spun Polypropylene Fibers on Molecular Weight Distri-bution Pp. 6 / 1-10, polypropylene spinning shows that It teaches that deterioration improves. These discoveries are important and are called (Degradation ratio), which leads to the determination of the fiber and spinning characteristics. Correlate to.   Branchesi and Balbi were held in November 1989, The plastics and Rubber Institute'sInternational ConferenceDepart at, line “Mechanical and Structual Properties of As-Spun Polypropylene Fil aments in Relation to Resin Rheology ”on pages 27 / 1-9 Applications of "controlled rheological" polymers have been found in high speed spinning operations I taught that.   Amos and Goldin, published October 19, 1993Internatio nal Fiber Journal , "Creating Higher Performan," published on pages 88-96. ce Fibers with a Novel Additive Concentrate ” Is a "visbroken" polymer or controlled rheology po It has been reported to improve fibers made from limers. These researchers Liquid or low melting point fractions can be added to the polyolefin resin used to make the fiber. Visbreaking or melt viscosity by adding Went down. This clearly gives a low molecular weight fraction, Fractions not only improve the fiber manufacturing process, but typically It appears to give a fibrous web with greater filtration efficiency than the treated resin.   Canich described in US Pat. No. 5,026,798 monocyclopenta. Film and resin prepared by dienyl-heteroatom transition metal complex catalyst system It has been taught that it can be used to make a variety of products including fibers. in this way The polymer prepared by the procedure described in column 9, line 53, has a concentration of about 1.5 to about 15 It is clear that it falls into the wide MWD range between. Kanichi, unfortunately, this For a particular wide range of molecular weight distributions, the question of where fibers can be produced economically And did not give suggestions. In addition, KANICH is a tree for producing satisfactory fibers. No direction is given regarding the treatment of fat. Therefore, this material has advantages for fiber formation. A rude opinion on usability is almost unprofitable in terms of enabling fiber production. It has no value.Summary of the Invention   The term "reactor grade" means that the molecular weight distribution (MWD) or polydispersity is polymerized. It means a polyolefin resin which is subsequently substantially unchanged. This term is special After the polymer is polymerized, 1) reduce the viscosity or substantially reduce the average molecular weight. Untreated or not exposed to treatment to reduce 2) MWD was substantially unchanged, but reduced viscosity or average molecular weight Means being treated or exposed to treatment. like that Reactor grade polyolefins are single-site catalysts, especially metallocenes. Molding of fibers, especially cross-section, when produced by a mold catalyst Alternatively, it is useful in forming diameter fibers. Polyols useful in the practice of the present invention Certainly untreated resin is preferable as a point of classification of fin polymer . The resin, which has been treated but has substantially the same MWD, is extremely functional. However, it is somewhat unfavorable.   Reactor gray with a narrow molecular weight distribution clustered around the nominal molecular weight of the polymer A non-ethylene polyolefin was produced.   A new fiber that outperforms other reactor grade polypropylene materials. It has been found that fibers can be produced from this polymer. The choice of polyolefin is eye Monomers which are preferably sotactic and have 3 to 10 carbon atoms. More preferably, it is derived from a monomer having 3 carbon atoms. The derived ones, polypropylene, are most preferred. These new fibers are the ultimate It has also been found that it can be incorporated into fabrics that exhibit excellent properties. In more detail, A small diameter, high strength fiber useful for It was also found that it can be manufactured from fins. These small diameter fibers are typical straight lines. Made of soft yarn or cloth that feels comfortable as it bends more easily than large diameter fibers Can be built. Such threads and fabrics have higher strength than expected. Demonstrate the additional unique advantage of doing.   Fabric cloths containing fibers made from polyolefins produced by monodentate catalysts Similar features include fibers made from reactor grade polyolefins as well It is particularly impressive when compared to other fabrics produced by various methods. These fibers And their fabrics are unique to conventional reactor grade polyolefins. Without some handling problems, as well as using post-reaction oxidative degradation polyolefins. It can be mass-produced at high speed without using it.   These fibers include Reactor Grade Isotactic Polypropylene, The polypropylene is a monodentate catalyst, especially for group 15 or group 16 element ligands. Or mono-, bis-, and tris-substituted or unsubstituted cyclopentadienyl ring transitions Metal compounds (each of which may be crosslinked or uncrosslinked as desired, or And optionally suitable activators, cocatalysts, scavengers, or combinations thereof. Manufactured by metallocene-type (MCN) catalysts that include a mixture of Melt flow rate (MFR) in the range of up to 5,000, and in the range of about 1 to about 3.5 It has a molecular weight distribution of MFR is a property known in the art and G / min or dg / min at 230 ° C as defined by MD 1238 (1) It is represented by. Preferred content combined with well-adjusted designation or average molecular weight The molecular weight distribution is based on the significant or low molecular weight fraction of the molecule. With the problems of conventional reactor grade or post-reaction oxidative degradation materials with either Enable the production of these fibers without interruption.   Fiber manufacturers will benefit if the average molecular weight of the polyolefin decreases. Can be. It is a treatment of polyolefins that achieves oxidative degradation, or molecular fragmentation. Can be achieved by It cuts many of the molecules that make up the polyolefin resin For post-reaction treatment with an oxidant such as an organic or inorganic peroxide. Polyolefins produced by conventional catalysts by exposing them to liolefins This can be achieved with the additional effect of shifting the MWD of the infin. Single seat High-grade polyolefin containing polypropylene, produced by metallocene type catalyst Oxidation causes many molecules to be cleaved by oxidation, but its molecular weight distribution (MWD) is A post-reaction treatment can be applied so that it remains substantially unchanged. Substantially MWD Made from a polyolefin treated in this way without any change Fibers and fabrics of such fibers are within the scope of the invention. Made with single seat catalyst An example of such a reaction aftertreatment of the prepared polyolefin resin is given later. Realize MWD Manufactured with a monodentate catalyst that can lower the average molecular weight without changing qualitatively The characteristics of the specified polyolefin resin are these polyolefins and, of course, Fibers, cloths and clothing manufactured from them are highly recyclable. Make it suitable.   These new fibers are used in melt spinning, spunbonding processes, and melt-blown processes. By the method of forming fibers from molten polymer containing wax or by centrifugal spinning (Centrifugal spinning), sheet cutting, and film fibrillation It can be formed by traditional methods.   Overall, the use of these various monodentate metallocene-type catalysts is supported. Reactions useful in the formation of fibers and subsequent fabrics, with or without Manufactures container grade polyolefin resin. Such fibers are conventional melt spun Fine fibers that can be produced with higher strength of the individual fibers, It can be spun across a wide range at high production rates. Immediately after producing fiber, spunbon Non-woven fabrics, including spunbonded or melt blown fabrics Can be blended with. These polymers are used in high-speed spunbondies. Forming smaller diameter fibers when used in the casting process, Therefore, it produces an overall softer fabric. This fabric has a traditional catalyst Similar spunbond made from manufactured reactor grade polyolefin. There is a larger number of finer fibers, especially at each bond point inside the fabric. Yes, in terms of the fact that it exists. Of course, different polymers according to the invention Made by blending with reactor grade polyolefin as detailed in Manufactured using manufactured fibers as well as pigments, antistatic agents, or other modifiers Fibers are also included within the scope of the present invention. Moreover, with traditional catalysts Blended with other materials including manufactured polymers, natural fibers, or other polymers. Fibers made from the combined reactor grade polyolefin of the present invention, and A resin produced by a mixture of media, wherein only one catalyst in the mixture is Fibers made from resins when considered to be monodentate under any of the conditions are also of the invention. It is within the range. As mentioned above, fiber manufacturers have You will also benefit from the processability.   When applied to the meltblown nonwoven process, fabric manufacturers should It would benefit from processability and could produce finer and stronger fibers. This For stronger and softer fabrics, but smaller for specialized applications Large number of regularly and evenly distributed fibers per fiber size and basis weight From which it will give better filtration capacity. Interfiber space where many fibers are smaller Which allows greater retention, especially for smaller particles.   Additional benefits include stronger, more flexible, softer fibers and fabrics Ability to make, and such fabrics include any kind of fabric including knits, fabrics, and non-woven fabrics. Of dough are included. Such features allow for the filtration or barrier layer of blood, vapor Various membranes, including membranes useful for filtration or permeation, such as body exchange media; daily wear or exercise And outdoor clothing, gowns, hats, face masks, foot or shoe covers or booties Medical or external such as booties, wraps, drapes, shirts, and pants In single-use, limited-use, or full-use clothing, including articles useful in family use. It is possible to use these fibers and cloths. These fine and soft fibers and These fabrics may have low blood strike-through or improved bacteria. It is useful when filtration of viruses and viruses is desired.   The flexibility of fabrics and cloths made using these fibers makes them suitable for diapers. And incontinence protection cover stock, inner liner, and feminine hygiene products, And make it useful for personal hygiene products such as reuse or disposable wipes. The fine diameter of the fibers and their ability to be fluffed make them suitable for blankets, surgical and clothing. Fee, personal pad or quilt, web, batting, Or make it useful in articles such as high loft fabrics. This The soft and tough properties of these fibers and fabrics make them suitable for furniture, automobiles, and gadgets. Useful as a cover for expensive or valuable articles, including lath products, and fabric softener Sheet, lotion or fragrance holding sheet, pest repellent or dust absorber support Makes it useful as a vehicle for various processes such as sheets.   The toughness, strength, and fineness of these fibers and fabrics (which give them a high surface area) , Other such as oil or chemical recovery or spill containment, in particular Makes it useful in absorbent applications. Toughness also depends on the cotton or rubber packaging, building Various wraps such as house wraps, as well as roadbed and soil Unique cloth like geotextiles useful for stabilization Contribute to utility in other industrial applications, including.   Other useful applications include thermal barriers and tobacco filters, thermal ventilation and Air treatment equipment such as air conditioning equipment, as well as water purification filters, Various filters are included, including air filter face masks. Other Applications include water separation from hydrocarbons, HEPA applications, and automotive air filtration. The excess is included. Other useful membrane applications include battery separators, utility Utility tarps and covers, and various tentings (ten ting) applications are included.   Cloths for many applications can be single ply or multi ply, either laminated or laminated. Such forms may be spunbonded / melt blown / spunbonded. Includes multi-layer morphology, other fiber / fiber composites, and film / fiber laminates . Multi-layer or composite fabrics are available in many ways or needlepunch and hide. A set of methods involving entanglement, such as Loentanglement Using an adhesive, by means of lacing, by thermal or ultrasonic means, Rum or adhesive layer, by solvent adhesion, and by electron beam, micro Includes waves and other electromagnetic means such as the use of radio frequency (RF) energy Can be combined by the use of radiation.Brief description of the drawings   FIG. 1 is a plot of take-off speed compared to fibers made from commercial polymers. 3 is a graph showing plotted tenacity and elongation.Detailed Description of the Invention   In the following, preferred embodiments and examples which illustrate and explain the present invention will be described. It However, these descriptions and examples do not limit the scope of the invention. And should not be so interpreted.   When used for the purpose of describing the present invention in the present specification and claims, " The terms "single-site catalyst" and "single-site catalysis" are true To be understood as meaning the state of catalysis using monodentate catalysis and monodentate catalysis Should be. With some apparently monodentate catalysts in the environment or under conditions of polymerization It is possible that some catalysts behave as if they were not monodentate. Such touch Media and catalysis are intended to be included in this term. Monodentate catalysts include, for example, Binding to Talocene and Metallocene Type Compounds (MCN) or Cocatalyst or Activator Ions Ionic species, metallocene mixture or mixture of metallocene type substances, and Mixtures, combinations, or single species selected from are included.   The present invention provides a reactor grade polyolefin produced by monodentate catalysis. Including fibers.   The present invention also relates to fibers containing reactor grade isotactic polyolefin or A cloth, wherein the polyolefin is produced by monodentate catalysis, Greater to about 5,000 melt flow rates and about 1.0 to about 3.5 Fibers or fabrics having a molecular weight distribution of   Generally, the preferred upper range of MFR is about 3,000, about 250, or depending on the method of formation. Is about 150. The preferred lower range of MFR is generally about 5, about 50, or about 100. It   As a general practice, the preferred MFR range for melt spinning is from about 5 to about 150. , The preferred MFR range for spunbonding is about 5 to about 250, and The preferred MFR range for melt blowing is from about 50 to about 3,000. Generally M of polymer The preferred upper limit of WD is about 3.5, about 3.2, about 3, about 2.5, or about 2.2. . The preferred lower limit of the MWD of the polymer is about 1.0, about 1.6, about 1.7, about 1.8, or Is about 2.0.   These fibers are traditionally weaved, knitted, and spun. Includes fibers by forming non-woven including bonding and melt-blowing processes It can be formed into a cloth. Fabrics made from these new fibers are especially Are of a smaller diameter, they have a better texture and are more Manufactured from similar fibers made from reactor grade polyolefins made in Drapability is superior to the woven cloth. The fibers of the present invention are manufactured with conventional catalysts. Melt-stretched to a smaller diameter than the reactor grade polyolefin This is especially true as it can.   Although not wishing to be bound by theory, we have found that Chain length consistency (narrow molecular weight distribution) and consistent tacticity of different polymers Due to the city distribution, the fibers of the present invention are even drawn to thinner diameters. No, generally stronger or have higher tenacity than conventional polymers Think. This reduces the fiber diameter while at the same time providing the extra strength of the fiber. Improved flexibility due to drilling; thereby improving the flexibility of the fiber Results in a fabric that can be made larger and that has improved drape and softness Means that. In general, finer fibers and their manufacturing processes are Will benefit. The diameter of the fibers produced gradually is about 400 μm, about 200 μm, About 100 μm, about 50 μm, about 20 μm, about 10 μm, about 5 μm, and about 3 μm . Coarse fibers benefit to some extent by the practice of the invention, while finer fibers Not as much as a profit to receive.   In addition, fabrics using such fine fibers will have significantly more fibers per basis weight. With fibers, especially in the case of meltblowing. This means that one such cloth Generally, the strength is higher, and if small holes or spaces are provided between fibers, Means something predictable. This feature is due to the overall strength of the fabric and the filtration of small particles. Both of these capabilities are particularly useful in filter applications where it is desirable.   In the last few years, several catalyst systems based on metallocene type compounds have been developed. These include Welborn's EP A 129 368, which is quoted. Are incorporated herein by reference. This patent is a catalyst for olefin catalysis. The use of clopentadienyl transition metal compounds is described. Turner And Hlatky EP A 277 003, EP A 277 004, and US Pat. No. 5,15. No. 3,157, which is incorporated herein by reference, contains metallocenes. A separate catalyst system based on silane-type compounds but using anionic activators has been described. There is. U.S. Pat.No. 5,057,475 to Kanichi, incorporated herein, A catalyst for olefin polymerization using a modified metallocene type catalyst, comprising: Cyclopentadienyl / heteroatom transition metal compounds were formerly metallocene compounds Generation-displacing catalysts are described. Kanichi, Flatkey, and Turner WO92 / 00333, which is also incorporated herein by reference, contains Ionic activators for the polymerization of amines with monocyclopentadienyl / heteroatoms It is described for use with transition metal compounds.   Specific metallocene-type catalysts useful in the production of isotactic olefin polymers Includes EP A 485 820, EP A 485 821, EP A 485 822, and And EP A 485 823, and Wellborn's U.S. Patents 5,017,714 and 5,120,867. Can be found in. These publications are hereby incorporated by reference. Incorporated in the book.   Various publications provide catalyst systems on supported media and use of the resulting supported catalysts Is described. These include Chang's US Pat. Nos. 5,006,500, 4, 925,821, 4,937,217, 4,953,397, 5,086,025, 4,912,075, And U.S. Pat. Nos. 4,808,561 and 4,897,455 to Wellborn. No. 5,077,255, No. 5,124,418, and No. 4,701,432, all of which Are incorporated herein by reference.   The following examples are for the preparation of isotactic poly-alpha-olefins. It is shown that a supported metallocene type catalyst is used. Use of supported technologies and supported catalysts Information on Burkhardt can be found in US Pat. No. 5,240,894 You can   The catalyst used for the following examples was used in a bulk liquid phase polymerization process However, the concepts related to the use of the catalysts presented herein include, for example, gas phase, slurry. It is also applicable to other polymerization processes, including single phase and high pressure processes.   Gel permeation chromatography (GPC) is based on the molecular weight of the polymer ( Widely used to measure MW) and molecular weight distribution (MWD) or polydispersity Liquid chromatography technology. This is a common and known technique. This Those features described here are measured using the widely practiced techniques described below. Decided Equipment and reagents used:     Waters 150C Chromatograph     3 Shodex AT-80M (mixed bed) columns     1,2,4-Trichlorobenzene as solvent (HPLC grade)     Polymer sample to be tested. Operating conditions:     Temperature: 145 ℃     Flow rate: 1 ml / min     Test time: 60 minutes     Injection volume: 300 microliters (μl) Sample preparation:     Samples are prepared by weighing 10 mg of sample into a 20 ml vial. Ten ml trichlorobenzene (TBC) was added and the mixture was stirred at about 180 ° C for the entire sun. Stir until the pull dissolves. This generally takes about 30 minutes. After that, turn off the solution. Transfer to sampler vial and place in 150 C GPC. calibration:     The results were fit to a third order calibration curve using narrow molecular weight standards. Calibrate the device by fitting. Standard is polystyrene and is indicated MW is obtained using the appropriate Mark-Houwink constant. Polyethylene equivalent weights. Data acquisition and evaluation:     With the data obtained, all calculations were installed on the VAX 6410 computer. Waters “Expert-Ease” software is used.                                     Example Example of catalyst Preparation of catalyst (including 6-step catalyst production and loading on inert media) rac-Dimethylsilane bis (2-methyl-4,5-benzoindenyl) zirconium Synthesis of dichloride Diethylmethyl (2-naphthylmethyl) malonate (1)   Dissolve 5.15 g (224 mmol) sodium in 150 ml absolute ethanol while heating And 37.3 ml (217 mmol) of diethyl methyl malonate was added at room temperature. 270 ml Of 50 g (217 mmol) 2-bromomethylnaphthalene (purity 96%) in ethanol The solution was added slowly dropwise at 0 ° C and the mixture was refluxed for another 4-5 hours. Heated for a while. It was poured into ice water and extracted with ethyl acetate. Organic together The phases were dried over sodium sulphate and evaporated. After drying under oil pump vacuum The oily residue was stirred with hexane at 0 ° C. to give 55 g (81%) of compound (1) Crystallized. Synthesis of 2-methyl-3-naphthylpropionic acid (2)   A solution of 23.7 g (422 mmol) of potassium hydroxide in 50 ml of water was added to 70 ml of ethanol. 33.2 g (105 mmol) of compound (1) in a solvent and the mixture is heated under reflux for 4 hours. It was After the solvent has evaporated, the solid residue is taken up in ethyl acetate, water is added and the salt The pH was brought to 1 with acid. The aqueous phase was extracted several times with ethyl acetate. Magnesium sulfate After drying over um, the combined organic phases were completely evaporated. Hexane residue And stirred to crystallize. The beige solid was placed at 175 ° C for decarbonation. And heated until gas evolution ceased. 21 g (94%) of product (2) beige Was obtained as a solid. Synthesis of 2-methyl-6,7-benzoindan-1-one (3)   22 ml of thionyl chloride was added to 21 g (98 mmol) of compound (2) to remove water. And the mixture was heated under reflux for 30 minutes. Then steam excess thionyl chloride. Emitted and removed. Volatile components are removed by leaving the residue under an oil pump vacuum for a short period of time. Then, in Ar atmosphere as an inert gas, dissolve in 25 ml of methylene chloride. Let it go. This solution was added to 26 g (196 mmol) of aluminum in 60 ml of methylene chloride. Slowly add dropwise to the suspension of the trinium trichloride and add the mixture for another 30 min. Heated at reflux. It was poured onto ice and extracted with methylene chloride. one The combined organic phases were dried over sodium sulphate and evaporated. Dark oily residue 60 Chromatograph on 0 g of silica gel 60. Hexane / eth as mobile phase Elute 8.6g (45%) of compound (3) using a mixture of luacetate (9: 3) I was able to do it. Synthesis of 2-methyl-4,5-benzoindene (4)   2.2 g (59.5 mmol) of sodium borohydride was added to 400 ml of tetrahydrofuran / 7.8 g (39.7 mmol) indanone, ie compound (3 ) Was added in portions at room temperature and the mixture was stirred for 14 hours. The solution in hydrochloric acid ice Pour onto the top and extract with ether. The combined organic phases are washed several times with water and washed with sodium sulfate. Dried over rium. The orange oil that remained after removing the solvent was washed with 240 ml of toluene. And 570 mg (3.15 mmol) p-toluenesulfonic acid at 80 ° C. Both were heated for 15 minutes. It is washed several times with water at room temperature and dried over sodium sulfate. It was dried and evaporated. The residue was chromatographed on 300 g silica gel 60. . Using a mixture of hexane / diisopropyl ether (20: 1) as mobile phase , 4.7 g (65%) of indene (4) could be eluted (colorless oil).¹ H-NMR spectrum (360MHz, CDCL₃): 8.02 (1, d), 7.84 (1, m), 7. 59 (1, d), 7.52 (1, d), 7.38 ~ 7.48 (2, m), 7.06 (1, m), 3.42 (2, s), 2.2 5 (3, d). Synthesis of dimethylbis (2-methyl-4,5-benzoindenyl) silane (5)   A solution of 10.2 ml (25.5 mmol) of 2.5 M butyllithium in hexane was added to 50 ml of tetraethyl. A solution of 4.6 g (25.5 mmol) of compound (4) in drofuran was added at room temperature and the mixture Was heated at reflux for 1 hour. This red solution is then added to 10 ml of tetrahydro. A solution of 1.55 g (12 mmol) dimethyldichlorosilane in furan was added dropwise at room temperature. The mixture was heated at reflux for 5-6 hours. Pour the reaction solution into ice water and Extracted several times with tell. The combined organic phases are dried over sodium sulphate and evaporated down. The residue was dried under oil pump vacuum. Black it on 300 g of silica gel 60. I went to the mattograph. Hexane / 3% ethyl acetate mixture as mobile phase Used, 500 mg of unreacted starting compound (4) could be eluted first. Riga Compound (5) of the same series followed with the same mobile phase. After removing the solvent, this The ligand system was crystallized (isomer) from hexane. Yield was 1.7g (34% , Or reacted indene, that is, 44% for the compound (4)). rac-Dimethylsilane bis (2-methyl-4,5-benzo-indenyl) zirconium Synthesis of mucichloride (6)   4.0 ml (10.2 mmol) of a 2.5 M solution of butyllithium in hexane was added to 20 ml of Inert at room temperature in a solution of 1.7 g (4.1 mmol) of compound (5) in hydrofuran It was added in an Ar atmosphere as a gas and the mixture was stirred at room temperature for 14 hours. Remove solvent The residue left after was dried using an oil pump vacuum and washed with hexane. The light brown powder obtained is used at an oil pump vacuum at 40-50 ° C for several hours. Dried, 1.0 g (4.0 mmol) zirconium tetra in 25 ml methylene chloride The suspension of chloride was added at -78 ° C. Warm the mixture to room temperature and then strip the solvent. 20 ml to rip and take out the meso form of metallocene, compound (6), It was extracted with toluene. The toluene extract residue is then treated with 40 ml of methylene chloride. Extracted. The solution was concentrated to a small volume and left at -35 ° C for crystallization. Combined A total of 970 mg (42%) of zirconocene compound (6) as pure racemate It was isolated in the same fraction. Racemic¹H-NMR spectrum (300MHz, CDCL₃): 7.96 (2, m), 7 .78 (2, m), 7.60 (2, d), 7.48 to 7.56 (4, m), 7.36 (2, d), 7.27 (2, s, b-Ind -H), 2.37 (6, s, Ind-CH₃), 1.36 (6, s, Si-CH₃). Mass spectrum: 574M⁺, Positive Correct disintegration, correct isotope pattern. rac-Dimethylsilane bis (2-methyl-4,5-benzo-indenyl) zirconium Preparation of supported catalysts of mudichloride and alumoxane   An 8-liter container equipped with a cooling jacket and an efficient overhead stirrer, Lumoxane (30% by weight, 925 ml) was added. Toluene (700 ml) with stirring A suspension of catalyst (5.0 g) in a nitrogen atmosphere with double-ended needle ). After stirring for 10 minutes, dehydrated silica (Davison 948, 800 ° C) Dried at 200 g) was added to the solution over 20 minutes. 10 minutes for slurry Stir for a while, then depressurize from the top of the container while₂A slight flow of I entered. The mixture was heated to 70 ° C. and the solvent was evaporated for 9 hours. Dried The solid was cooled to ambient temperature overnight. Isopentane (5 liters) added to solid Was slurried and the mixture cooled to 0 ° C. Add ethyl acetate to the stirred mixture. 8.5 to 17 liters / minute (0.03 to 0.06SCF) through a dip tube / Min) was added until a total of 491 liters of ethylene were added. Stirring Was stopped and the solid was allowed to settle. Decant a liquid from a solid, This And washed twice with 1.5 tonnes of isopentane. N the wet solid₂Dry in the atmosphere Transferred to a box and filtered through a # 14 mesh sieve. Fine grain The pups were filtered off, washed with pentane (4 liters) and dried in vacuum. Yield: 326 g.Polymerization example Laboratory-scale polymerization data for supported catalysts.   Pre-flushed with nitrogen, heated to 65 ° C, and triethylaluminium 2 liters of methanol (0.5 ml of a 1M solution in hexane) and propylene (1000 ml). A sample of the catalyst of Example 1 slurried in an autoclave in hexane (2 ml). (199 mg) was poured with propylene (250 ml). The reaction was run for 1 hour. Auto The clave was cooled, evacuated and opened. Inspecting the interior of the reactor is clean and dirty. Turned out not. The polymer product was dried in vacuum. 305g of smooth A granular isotactic polypropylene (iPP) product was obtained. Mw is 27 The bulk density was 3,000, the bulk density was 0.43 g / cc, and the average particle size was 750 μm. Large-scale production of isotactic polypropylene using supported catalysts   The polymers used in the examples of the present invention were continuous type, single reactor, bulk liquid phase. Made in a polymerization process. To the reactor, stirrer, and to remove heat of reaction I put on the jacket. The reactor temperature was set to 65 ° C and 1.3g of catalyst was placed in the reactor. Feeded at catalyst / hour rate. Propylene into the reactor at a rate of 60 kg propylene / hour Supplied. Control the molecular weight of the product using a continuous stream of hydrogen (0.75g hydrogen / hr) I controlled. Under these conditions, the average residence time of the catalyst inside the reactor was 4.0 hours. It was. Under these conditions, polymer was produced at a rate of 9.1 kg polymer / hour. Living The product had an MFR of 22 (230 ° C / 2.16 kg).Examples of fiber and fabric formation   It is spun by mechanically pulling a bundle of fibers from the extruded melt. Flat (non-lustre or low raster), partially stretched The fibers were manufactured as partially oriented yavns (POY). This This is J. J. Jenkins, Inc. (Sterlin) This was done on a fiber production line assembled by Starllings, NC. This line is a 5 cm (2 inch) Davis Standard push Deliverer (having a length / diameter ratio of 30: 1) and a length / diameter ratio of 1.2 of 0.6 mm 7 6cc / rev Zenith (Z) extruding molten polymer through a spinneret plate with 2 holes enith) consisted of a metering pump. I used a light pump speed of 10 rpm, A throughput of 0.625 g / hole / min was given.   By axially spinning unheated godet, 1 Fiber from melt at 232 ° C (450 ° F) at 000, 1500, 2000, 2500, and 3300 m / min Was stretched. Fibers expressed as total denier / total filament collected at each speed The bundles of fibers were 405/72, 270/72, 203/72, and 162/72, respectively. 5 minutes The bundle of fibers was collected by a Leesona winder for analysis as a run. It was   Fiber bundle tenacity (g / denier) and elongation are measured by Instron ron) until it breaks. Textile testing is syntech ・ Sintech Sima (Testwork II^-) Computerized for material testing Instron device connected to an Instron computer that supports the system, 11 It went on 22 type. Instron Pneumatic Cord and yarn Yarn Grips (Model 2714) were used to grab the sample. 2.5 cm 500m sample with (1 inch) gauge and 0.1g preload It was pulled at a rate of m / min until it broke. Break sensitivity is 95 of force % Was a decrease.   Fibers were melt spun from polypropylene with MFR of 40, 51, and 68. these Is a material produced by the metallocene type catalyst described above. Controlled reoro Made by conventional catalyst with MFR of 33, which has been subjected to gee treatment (oxidation deterioration after reaction) Made polypropylene (PP-3445 manufactured by Exxon Chemical Company) ) And a conventional catalyst having an MFR of 35 that has not been post-reaction oxidized. Produced polypropylene (PP-334 manufactured by Exxon Chemical Company) Fibers spun from 5) were used for comparison. The following results are 1000, 1500, 2000 , Obtained from the tenacity and elongation of fibers spun at 2500 and 3300 m / min draw speeds It is a thing. The results of these tests are shown in Table I.   These results and a graph showing these results (this is shown in Figure 1) ), The polyolefin porosity produced by the metallocene type catalyst system Fibers made from limers are more prominent than fibers made using control materials. It is clear that the performance is excellent with respect to the strength tested. Fiber elongation In some cases, fibers of materials produced by monodentate catalysts are produced by traditionally produced polypropylene. It is clear that it has different performance than the fibers of pyrene resin. After melt spinning , Test fibers of the present invention were produced by conventional catalysts and were not oxidatively degraded. Re It is more related to the diameter of the final fiber than the control fiber made from propylene. At a given take-off speed, it retains less elongation but is generally stronger. It is clear that they form fibers. In all cases, as a control for comparison The resin used was obtained from Exxon Chemical Company and Those with MFR are publicly available. Manufactured by metallocene type catalyst The obtained resin was obtained as described above.   Without wishing to be bound by theory, these results indicate that the fibers are melt-formed. Produced by a monodentate catalyst as more force is applied. It also appears that the strength of the fibers of the tin is significantly increased. This is As the rolling speed increases, the fiber diameter decreases and a greater degree of stress is applied to the fiber. It is easy to see by recognizing the fact that is given to. Tested practice Example fiber has significantly higher tenacity than either control at high take-off speeds It is clear that Reactor grade polypro produced by conventional catalyst The strength of pyrene fibers even tends to deteriorate as more force is applied. The fiber cannot be formed due to the breakage of the fiber during the take-up. This is for fiber manufacturers Is an important advantage because of its smaller diameter and therefore more flexibility. You will benefit from being able to make fibers. Surprisingly, these The finer fibers of, contrary to intuition, also have a higher tenacity. Reactor-grade membrane This newly discovered fiber formed from a polymer produced with a talocene-type catalyst The feature, therefore, is the ability to form finer fibers with less material required. Empowering, these fibers are more flexible due to their greater flexibility, And stronger, and faster to produce, thus a great combination of advantages Providing mats to fiber manufacturers.   Higher take-up during the formation of the fibers of the present invention and, optionally, subsequent formation of the fabric. Fiber velocity, that is, by generally stressing the fibrils, It is clear that the strength of can be improved. Investigate and understand these benefits gained However, in order to standardize the standard of these advantages, we focused on the application of stress in the final fiber. It was Extruded through a spinneret or die with holes having a diameter of 600 μm or Melt drawn fibers were formed by drawing. The diameter of the strongest fiber is It was much smaller than the diameter, ie the initial formed diameter. Initial formed diameter to final diameter of fiber Dividing by gives what is called the "final draw reduction". Be done. At a take-off speed of 1000 m / min, the final fiber diameter was 29.3 μm, The phase formation diameter was 600 μm. Final draw reduction (FDR) for this fiber is 600 It is 20.3, which is derived by dividing μm by 29.3 μm. Wind up at 1500 and 2000 If the same calculation is carried out for fibers that have been taken or taken, the FDR will be 24 .7 and 28.8.   Looking at the results of the tenacity test shown in Table I, the final drawing reduction greater than about 20 Manufactured from reactor-grade polymers manufactured by monodentate catalysts with low values Fiber made from reactor grade resin made by conventional catalyst It is clear that it is considerably superior in performance to the similar fiber. Powerful test Based on the evaluation, an improved tenacity was produced with a take-off speed of about 500 m / min (single Fibers made from reactor grade polyolefins made by suppository catalysts It is thought to be found in. Because the diameter is reduced and the tension The application of force to increase the dura, i.e. the addition of stress, depends on this spinning speed. Because it can be achieved. 1000, 1500, 2000, 2500, 3000, and 3300m / min A higher take-up rate of γ would be more preferable. However, this The application of force to obtain these benefits can be achieved in a number of ways and Is a process for fiber production, and immediately after including meltblowing and spunbonding It is clear that the fabric forming process, as well as the melt draw process shown, are included. ItExample of spun bonding   Another test was performed to form fibers and produce spunbonded nonwovens. This This is a 1 meter line made by the Reifenhauser Company. This was done using the Reicofil line. The size of the extruder is 7 cm (2.75 Inches) and had a length: diameter ratio of 30: 1. 3719 die plate holes And each had a diameter of 0.4 mm and an L / D ratio of 4/1. Table I is test Polymers, processing conditions for each tested polymer, and spa manufactured It gives general information on the test results of bonded non-woven fabrics. Spunbondin Gupro Seth is one of the well known methods in the field of fabric manufacturing. In general Continuous fibers are extruded, placed on an endless belt, and tied together. However, this is often done with heated calender rolls. Yes. Overview of Spunbonding, Knoxville, University of Tennessee , Sponsored by TANDEC,Eighth Annual Nonwovens Workshop, 1990 July 30th-August 3rd, Wadsworth, L .; C. and Goswami, B .C. Non-woven fabric, obtained from the "Spunbonded and Melt Blown Processes" bulletin.   Spunbondin is a polypropylene resin produced with three metallocene type catalysts. The two control materials were also tested. Control examples It had a melt flow rate (MFR) of 70 and an MFR of 35. For comparison test The first two monodentate catalysts tested to use materials of similar nominal molecular weight The resins produced were of 68 MFR and 45 MFR, respectively. Third test Is for spinning fibers and forming non-woven fabrics from resins made with 22 MFR monodentate catalysts. there were. Two tests each with a melting temperature of 210 ° C (410 ° F), the other with 2 Performed at a melting temperature of 38 ° C (460 ° F).   These tests are conducted between spanned dead fibers and fabrics formed at different temperatures. This was done to find the differences. Fiber diameter measurements and final spa The results of these tests, including the machine direction (MD) tensile strength of bonded nonwovens, It is shown in Table II below. 40g / m for all tested fabrics²Basic weight of (b asis weight).   From this set of test data, made from resins made with monodentate catalysts Fabrics made from smaller diameter fibers are consistently stronger than control fabrics I understand. This is especially apparent when the fibers are formed at about 240 ° C. Cloth manufacturing Can produce stronger fabrics with smaller diameter fibers Receive a profit. By practicing the present invention, a fiber manufacturer may simply Careful selection of resin, with very few process or equipment modifications, This can be achieved.Example of melt blowing   By producing fibers using the melt-blowing process on the same material Another experiment was conducted. Melt blown technology is used in the manufacture of non-woven fabrics. This is a well-known technique in the field. This process is outlined in “Melt Blown Pro cess ”,Melt Blown Technology Today, Miller Freeman Publications, Inc., San Francisco, California, 1989, pages 7-12. This test , 51 cm (20 inches) Accurate Products Melt Blow (Accurate P roducts Melt Blown) production line. The extruder has a 30: 1 length: It's a 5 cm (2 inch) Davis Standard with a diameter ratio It was. The die nozzle had 501 die holes. Diameter of each hole Was 0.4 mm (0.015 inches). The die length is 15: 1 and the air gap is 0.15mm (0.06 0 inch). Exxon Chemical Company is the traditional material for comparison And obtained by MFR. The other tested resins are listed above. It was a polyolefin produced by a monodentate catalyst. Melt Blown Example I   Samples of two poly-alpha-olefins, more particularly metallocene-type catalysts A polypropylene polymer, which was polymerized with a medium, was formed into a meltblown fabric, which was then treated with a peroxide. Polypropylene (3545G) prepared with a conventional titanium chloride catalyst 400MFR with 750ppm peroxide, exon with 750ppm peroxide (Obtained from Chemical Company) was also formed into a meltblown fabric. Forming a cloth To determine the polymer properties of the polypropylene used to It is shown in Table III.   Air permeability is similar to ASTM D737-75 and FTM'S 191 Method 5450-1-1970, INDA standard. Measured using the quasi-test IST 70.0-70 (R82). Measured by M.D., Gaithersburg, A permeability test from the Frazier Precision Instrument Co. of Oakmont Ave., 210. It carried out using the test machine (Permeability Testing Machine).   The fabric of Sample I is 35.66 m, as can be easily seen.³/ Min (min) / m²of 17.99 m compared to the relatively open structure of the control fabric which has a value³/ Min / m²sky of It has an air permeability value. The MFR of sample I is slightly higher than the control polymer , Therefore its molecular weight is slightly lower, but the difference is that it is a large phase in air permeability. Too small to explain the difference.   Sample II has a much higher MFR and lower molecular weight than Sample I and the control. To do. The cloth of sample II is 15.86m³/ Min / m²Has an air permeability value of Much lower than the control value and only slightly lower than sample I. Departure The improved air permeability in the two bright materials results in improved filtration efficiency and barriers. Must correlate with characteristics. This is produced by single seat catalysis (SSC) Means that more and smaller particles are retained on the filtered filter To do. Melt Blowing Example II   Three different meltblown fabrics were made using two polypropylenes. One of the polypropylenes was polymerized by a monodentate metallocene type catalyst. The second is a conventional peroxide-treated (750ppm) catalyst (titanium chloride). Made of polypropylene (400MFR) (3545G, 750ppm peroxide) 400, obtained from Exxon Chemical Company). For each polymer The conditions for melt-blow processing are: 1) highest coverage, 2) highest Apparent air permeability, 3) lowest shot, and 4) softest texture Was optimized to produce webs or mats having "Shots" are generally Described as "lint and polymer grains" in the final fabric. Shot of Occurrence is present because it is a defect in the fabric and the fabric containing excess shots is unusable Is not desirable.   Among the important processing conditions, including air velocity and air temperature, we have found that It has been discovered that extrusion temperature is the most important condition to offset the end cloth properties. Polymers (materials made with monodentate catalysts) useful in the practice of this invention are 232 ° C (4% Excellent fabric was formed at 50 ° F), but the control is more Higher temperatures were required, i.e. 254 ° C (490 ° F). It has already been explained in the description of the present invention. As it became easier, 1) less energy consumption during manufacturing, 2) die Longer life, and 3) less evaporation of low molecular weight molecules, and Many advantages, including others, are offered to fiber and fabric manufacturers.   By applying a light water mist to the molten polymer stream between the die and the recovery device It is known that the properties of shot-containing fabrics are improved (US Pat. No. 3,959,42). ). As shown in Table IV, of the conventional polypropylene (PP) control fabric The properties were significantly improved by a water mist, but were manufactured using a water mist quench. Fabrics made from a single-catalyzed polymer made from It remains. Therefore, here again, fibers and fabrics with improved practice of the invention may be provided. Manufacturing and simplifying the manufacturer's process, thereby reducing costs. And are shown.   Most available polyolefins are the most available for testing against the fabrics of the present invention. In order to produce a viable cloth, in interpreting the qualitative results of this experiment, It is helpful to understand the following:   The texture (hand) is a measure of the softness of the cloth. In this test, Subjective comparisons were determined by technicians using the gloved-hand feel .   The coverage holds the cloth in front of the backlit glass. , Was evaluated by grading the uniformity and light transmission of the fabric web.   The shot crosses the width of the cloth held in front of the backlit glass. It was determined by evaluating the amount of shots being shot.   Table V provides more quantitative data on the use of meltblown fabrics in filtration applications. Is shown. Commercially available, available from Exxon Chemical Company PD3545G is a particulate polypropylene with a peroxide coating. That The MFR is in the range of about 1100. In Table V, this material is A comparison against common oxidatively degraded polyenes made specifically for high speed production Used as a control example. The test polymer was made with a monodentate catalyst as described above. I made it.   Table V shows three comparisons. MB1 and MB2 are commercial rates of 0.8g Figure 3 shows test results for fabrics made with / hole / min. Controls and tests The MFR of the cloth was about 1100, which was in good agreement.   MB3 and MB4 use the same polymer with matching MFR. This trial The difference between the test and the previous test is that in this test, rather than matching the production rate The polymer was tested at the optimum speed for fabric quality. This purpose is The most probable is to produce a control fabric for comparison against the fabric.   The third comparison in Table V uses the optimal production rate and was used to make test fabrics. Change the MFR of the polymer used.   As can be seen from these three tests, the fabric of the present invention was tested in each of the three comparisons. Performance is superior to the control. Lower air permeability and higher filtration efficiency (file Produced at commercial rates, as indicated by the amount of material retained on the luther). Of the present invention (MB1) produced is superior to the control (MB4) produced at optimal speed Is interesting.   A particularly interesting result is the use of polymers with different MFR to Seen in the third comparison made (MB5, MB6, and MB7). Than Clearly, a high MFR will benefit. MB6 1250 MFR Further peroxide degradation of polymers made with commercially available conventional catalysts This is of particular interest when it is understood that it can only be obtained by. This is , There are additional single chain low molecular weight polymer molecules in such degraded polymers Means to do. This causes more pronounced drooling, smoke, and low molecular weight terminal Cause evaporation. The fabric of the present invention is softer and has an even distribution of fibers It is more uniform and has better filtration properties, but this is Better than traditional fabrics that have poor manufacturing properties as well as manufacturing process imperfections That is clear.   Volunteers who agree to expose themselves to toxic substances (a patent lawyer Smoking through a piece of cloth held on the edge of the cigarette (registration number not shown) Another quantitative test for air permeability and retention of contaminants by . In this double blind test, volunteers use the fabric of the present invention I couldn't breathe in after I puffed it three times, but it was a control cloth (quenched with a mist of water. It was reported that one cigarette using the same) could be completely sucked out. This The result of is in agreement with the result of the repeated test, and is in agreement with the measured result. This A small test of vividly demonstrates the effectiveness of the fabric of the present invention in retaining particles. This shows the practical value of the present invention. Changes in MFR without substantial changes in MWD   As mentioned above, polymers produced by monodentate catalysts have a lower average molecular weight. In order to control or adjust the deterioration, especially the oxidative rheology. . This means that some post-reaction treatments can be applied to the molecular weight distribution or Reduces melt viscosity without substantially changing polydispersity and melt flow rate Means that can be increased. This test example shown in Table VI , Show characteristics not obtained with polymers produced by conventional catalysts. PD3702G is a polyolefin obtained from Exxon Chemical Company . The SSC polyolefin was produced by the same method as described above, It represents a polyolefin produced by a medium.

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, DE, DK, ES, FR, GB, GR, IE, IT, LU, M C, NL, PT, SE), AU, CA, CN, JP

Claims (1)

[Claims] 1. Fibers Containing Reactor Grade Polyolefin Produced by Monodentate Catalysis . 2. A fiber comprising reactor grade poly-alpha-olefin, the poly-alpha Melt flow rate of rufa-olefin in the range from 0 to 5,000 dg / min A fiber having a MWD in the range of 1-3. 3. The fiber of claim 1 or 2, wherein the polymer has a MWD in the range of 1.6 to 3. 4. Any of claims 1 to 3 wherein the polymer has a MWD in the range 1.7 to 2.8. The fiber of claim 1. 5. Any of claims 1 to 4 wherein the polymer has a MWD in the range of 1.8 to 2.5. The fiber of claim 1. 6. Any of claims 1 to 5 wherein the polymer has a MWD in the range of 1.8 to 2.2. The fiber of claim 1. 7. The polymer has a melt flow rate in the range of 5 to 3,000. 7. The fiber according to any one of claims 1 to 6. 8. A method according to claim 1 produced by forming fibers from molten polypropylene. A fiber according to any one of claims 1 to 7. 9. Fusing to at least one forming device having at least one fiber forming opening Formed by passing polypropylene and simultaneously or subsequently solidifying The fiber according to any one of claims 1 to 8, which is Ten. 10. Any one of claims 1-9 formed in a melt spinning process. Fiber. 11. Formed in the melt-spinning process and then mechanically wound after or at the same time The fiber according to any one of claims 1 to 10. 12. 13. The polypropylene of claim 1 to 12, wherein the polypropylene has an MFR in the range of 5 to 150. The fiber according to claim 1. 13. 14. Any of claims 1-13 formed by movement of a liquid other than the molten polymer. The fiber of claim 1. 14. 14. Any of claims 1-13 formed in a spunbonding process. The fiber of claim 1. 15． 15. The polypropylene of claim 1, wherein the polypropylene has an MFR in the range of 5-250. The fiber according to claim 1. 16. 16. The method according to any one of claims 1 to 15 formed in a melt-blowing process. Term fiber. 17． A polypropylene according to any one of claims 1 to 16, wherein the polypropylene has an MFR in the range of 50 to 3000. The fiber according to claim 1. 18. A contract according to any one of claims 1 to 17 having a diameter in the range of 18.1 to less than 50 μm. Required fiber. 19. A contract according to any one of claims 1 to 18 having a diameter within the range of 19.3 to less than 20 μm. Required fiber. 20. A fabric containing fibers comprising reactor grade isotactic polypropylene. Thus, polypropylene is produced by monodentate catalysis and is greater than 0 to 5,000 dg. Fabric with a melt flow rate in the range of 1 / min and a MWD in the range of 1 to 3.5 . twenty one. 21. The fabric of claim 20, wherein the polymer has a MWD in the range 1.7-3. twenty two. 21. The polymer according to claim 20, wherein the polymer has a melt flow rate in the range of 5 to 2000. The cloth according to any one of claims 21 to 21. twenty three. 23. Any of claims 20-22, comprising fibers formed from molten polypropylene. The cloth of claim 1. twenty four. 21. Manufactured by a spon bonding or melt blow process. 24. The cloth according to any one of claims 23 to 23. twenty five. A fiber comprising isotactic poly-alpha-olefin, comprising poly- Alpha-olefin   a) produced by monodentate catalysis,   b) after the reaction, i) a treatment for fragmenting the molecule, or ii) poly-alpha- Substantially not undergoing treatment to reduce the viscosity of olefins,   c) has a melt flow rate in the range of greater than 0 to 5000 dg / min, and   d) having an MWD in the range of 1 to 3.5, or   a) produced by monodentate catalysis,   b) post-reaction treatment for i) molecular fragmentation or ii) viscosity reduction Have received,   c) has a melt flow rate in the range of greater than 0 to 5000 dg / min, and   d) have an MWD in the range of 1 to 3.5, which MWD is Fiber that has not changed qualitatively. Melt flow rates in the range of greater than 26.0 to 5,000 dg / min and ranges from 1 to 3 Fibers of isotactic poly-alpha-olefin resin with MWD within enclosure And a method for producing a non-woven fabric from the fiber, if desired,   a) alpha-olefins as isotactic poly-alpha-olefins With a catalyst capable of forming a catalyst for a sufficient time and temperature under the reaction process conditions. The process of   b) forming an isotactic poly-alpha-olefin,   c) recovering the desired isotactic poly-alpha-olefin,   d) producing poly-alpha-olefin by melting poly-alpha-olefin The process of transferring to a device that can be built,   e) forming fibers from molten poly-alpha-olefins,   f) simultaneously or subsequently solidifying the fibers, and   g) collecting the resulting fibers or further processing the fibers to form a fabric ,   Including the method. 27. A composite or laminate comprising fibers or fabrics produced by one or more methods 25. The fabric of any one of claims 20 to 24 formed by: 28. A laminate or composite comprising spunbonded fabric and meltblown fabric, claim Item 27 cloth. 29. A laminate or composite comprising spunbonded fabric and meltblown fabric, claim Item 28 cloth. 30. The MWD of the poly-alpha-olefin is within the range of 1.7 to 3, and the MFR is 11. The fiber of claim 10, wherein is in the range 5 to 250. 31. 31. The fabric of claim 30 formed by knitting or weaving. 32. Machines at speeds greater than 1500 m / min so that the final stretch reduction value is greater than 20. Claims made from molten poly-alpha-olefins using mechanical winding The fiber according to any one of items 1 to 19, 25, and 30 to 31. 33. The fibers are melt-spun and spun at a speed such that the final draw reduction is greater than 20. 27. The method of claim 26, wherein: 34. The fiber of claim 25, produced in such a way that the final draw reduction value is greater than 20. Wei.